Subject: Re: CCL:Paramagnetically shifted 1H NMR spectra

From: Arvydas Tamulis <[email-masked]>
Date: Tue, 13 Feb 2001 09:12:56 +0200 (EET)

Dear Dauoglas Fox and other Netters who responded me during last days
concerning calculations of paramagnetically shifted 1H NMR spectra
possessing up to 135 ppm values.

During last days I clearified that for large (100 ppm) paramagnetic
1H shifts are responsible not good basis sets (only few ppm) and not
electron correlations (only tens ppm) but including relativistic effects:
'electron spin-orbit', 'electron spin-spin', and 'electron spin - proton
spin', etc. couplings. I do not know what relativism it is included in DALTON
and DIRAC packages (maybe here can respond experts from these teams) but
for my opinion if it is included 'electron spin - proton spin' coupling
that should give these 100 ppm paramagnetic shifts in 1H NMR spectra.

Maybe in other programs people are doing such a inclusions of
'electron spin - proton spin couplings'?
I would be appreciate if somebody will allow me to perform trial calculations
of biliverdin CuOEB molecule 1H NMR spectrum using DALTON, DIRAC or other
program with implemented as much as possible relativistic effects.

Thanking your in advance for further discussions and advises.

Yours sincerely, Arvydas Tamulis
Enclosed please find X-Ray geometry of CuOEB molecule in Angstroms:
 Cu1                   0.        0.        0.
 O2                    0.2239   -2.96653  -1.55039
 N3                    1.38133  -1.33544  -0.35323
 N4                    1.38119   1.34207   0.36885
 C5                    1.22628  -2.58553  -0.97483
 C6                    2.51385  -3.33756  -0.86868
 C7                    3.37827  -2.55016  -0.22896
 C8                    2.67395  -1.28282   0.09472
 C9                    3.26426  -0.17877   0.65202
 C10                   2.68854   1.08761   0.70813
 C11                   3.38244   2.34651   0.96318
 C12                   2.50269   3.34699   0.72477
 C13                   1.25013   2.71593   0.35196
 C14                   0.0751    3.37078   0.
 C15                   2.68652  -4.68205  -1.49633
 C16                   3.05674  -4.56912  -2.96369
 C17                   4.84657  -2.77602   0.04178
 C18                   5.72923  -2.08939  -1.00856
 C19                   4.85471   2.43112   1.27447
 C20                   5.69449   2.34802   0.0041
 C21                   2.72592   4.83225   0.72854
 C22                   2.87181   5.41601  -0.67222
 H23                   4.13917  -0.29105   1.00274
 H24                   0.09707   4.35684   0.
 H25                   1.8737   -5.18468  -1.40342
 H26                   3.37402  -5.20107  -1.07412
 H27                   3.13618  -5.45897  -3.37019
 H28                   2.36288  -4.06322  -3.3895
 H29                   3.87718  -4.07992  -3.05734
 H30                   5.00432  -3.74715   0.00503
 H31                   5.07799  -2.46117   0.91361
 H32                   6.64112  -2.28581  -0.82449
 H33                   5.51113  -2.4159   -1.88189
 H34                   5.58593  -1.11668  -0.96462
 H35                   5.10459   1.68705   1.84642
 H36                   5.03303   3.27735   1.73233
 H37                   6.61722   2.41078   0.21711
 H38                   5.52484   1.4978   -0.44582
 H39                   5.45344   3.10135  -0.56135
 H40                   3.50226   5.01567   1.24612
 H41                   1.98737   5.25961   1.1645
 H42                   3.01354   6.38803  -0.58859
 H43                   3.62122   5.00544  -1.10604
 H44                   2.09038   5.25163  -1.1876
 N45                  -1.43943  -1.27259   0.35323
 N46                  -1.32005   1.40226  -0.36885
 C47                  -1.12793   2.76892  -0.35196
 C48                  -1.34022  -2.52835   0.97483
 C49                  -2.72843  -1.16245  -0.09472
 C50                  -2.63743   1.20627  -0.70813
 C51                  -2.35113   3.45514  -0.72477
 O52                  -0.3558   -2.95361   1.55039
 C54                  -2.66     -3.22228   0.86868
 C55                  -3.4885   -2.39716   0.22896
 C56                  -3.26899  -0.0332   -0.65201
 C57                  -3.27458   2.49484  -0.96318
 C58                  -2.50799   4.94886  -0.72854
 C59                  -2.89238  -4.55775   1.49633
 C60                  -4.9654   -2.5574   -0.04178
 H61                  -4.14802  -0.1064   -1.00274
 C62                  -4.74161   2.64493  -1.27447
 C63                  -2.62775   5.53854   0.67222
 H64                  -3.2754    5.16668  -1.24612
 H65                  -1.75115   5.34291  -1.1645
 C66                  -3.2572   -4.42844   2.96368
 H67                  -2.10276  -5.09608   1.40342
 H68                  -3.60232  -5.04563   1.07412
 C69                  -5.8166   -1.83214   1.00856
 H70                  -5.16625  -3.52054  -0.00503
 H71                  -5.18257  -2.23255  -0.91362
 C72                  -5.58426   2.59932  -0.0041
 H73                  -5.02439   1.91273  -1.84642
 H74                  -4.88207   3.49828  -1.73233
 H75                  -2.72604   6.51592   0.58859
 H76                  -3.3947    5.16177   1.10604
 H77                  -1.85441   5.33953   1.1876
 H78                  -3.37619  -5.31387   3.37019
 H79                  -2.5415   -3.95395   3.3895
 H80                  -4.05504  -3.90319   3.05734
 H81                  -6.73633  -1.98774   0.82449
 H82                  -5.61326  -2.16804   1.88189
 H83                  -5.63012  -0.86678   0.96462
 H84                  -6.50328   2.70312  -0.21711
 H85                  -5.45265   1.74239   0.44582
 H86                  -5.3099    3.34117   0.56135
***********************************************************

On Mon, 12 Feb 2001, Cust. Service Doug wrote:

>
>    Dr. Tamulis,
>
>    I don't have ready access to this journal at my office.  Can
> you send the structure you used?  Have you verified that the
> environment around these protons is reasonably described by this
> input structure?
>
>    Generally the shifts in proton NMR calculations are good only to
> about 10% which makes them less appropriate for structural studies
> but the wide range you report from the experiment should be reproduced
> at least qualitatively.
>
> >
> > Dear Netters,
> >
> > We did not succeeded to calculate paramagnetically shifted 1H NMR spectrum
> > of biliverdin molecule CuOEB using Gaussian 98 (see experimental data in
> > J. Am. Chem.Soc., vol. 115, p. 12206 (1993)).
> >
> > We have optimized geometry of TeMeSilane molecule and obtained from NMR
> > calculation the Isotropic Shielding values for H atoms (in ppm):
> >
> >    H    Isotropic =    31.9027   Anisotropy =     9.6413
> >    XX=    29.4642   YX=     0.2951   ZX=    -0.7329
> >    XY=     0.4642   YY=    32.9871   ZY=    -5.1492
> >    XZ=    -0.8947   YZ=    -5.1015   ZZ=    33.2567
> >    Eigenvalues:    27.9348    29.4430    38.3302
> >
> > We have used Density Functional Theory B3PW91/6-311G**
> >
> > We have taken geometry of CuOEB from X-Ray experiment.
> > Our B3PW91\6-311G** calculated CuOEB NMR  Hm shielding values (ppm):
> >  23  H    Isotropic =    28.4781   Anisotropy =    10.0683
> >    XX=    24.0637   YX=    -1.2135   ZX=     -.8179
> >    XY=     -.0906   YY=    35.1141   ZY=    -2.2717
> >    XZ=     9.0739   YZ=     1.6948   ZZ=    26.2566
> >    Eigenvalues:    20.8808    29.3633    35.1904
> >
> >  60  H    Isotropic =    27.5216   Anisotropy =    12.3793
> >    XX=    22.4061   YX=     2.7621   ZX=    -1.0495
> >    XY=     -.3733   YY=    35.4454   ZY=     2.7019
> >    XZ=    10.0293   YZ=    -6.4196   ZZ=    24.7134
> >    Eigenvalues:    18.6646    28.1258    35.7745
> >
> >  and shielding Hm' value:
> > 24  H    Isotropic =    25.8868   Anisotropy =    16.3237
> >    XX=    36.5750   YX=     -.6396   ZX=     4.7813
> >    XY=     -.0379   YY=    23.9614   ZY=      .1694
> >    XZ=     -.9100   YZ=     2.3766   ZZ=    17.1241
> >    Eigenvalues:    16.7005    24.1907    36.7693
> >
> > It means that our calculated chemical shifts for Hm and Hm' are equal to
> > few ppm while CuOEB experimental NMR chemical shift values for Hm and Hm' in
> > J. Am. Chem.Soc., vol 115, p. 12206 are equal approximately to 135 ppm and
> > -100 ppm.
> >
> > Why so badly we have calculated paramagnetically shifted 1H NMR spectrum
> > for CuOEB molecule?
> > Maybe GAUSSIAN is not able to calculate paramagnetically shifted 1H NMR
> > spectra?
> > Which program is suitable for calculations of paramagnetically shifted 1H
> > NMR spectra?
> >
> > Thanking your in advance.
> > With best regards, Arvydas Tamulis & Jelena Tamuliene
> > *******************************************************
> >            Arvydas Tamulis
> >
> > Doctor of Natural Sciences, senior research fellow
> >
> > Institute of Theoretical Physics and Astronomy,
> > Theoretical Molecular Electronics Research Group,
> > A. Gostauto 12, Vilnius 2600, Lithuania
> > e-mail: [email-masked]; WEBsite: http://www.itpa.lt/~tamulis/
> > fax: +(370-2)-225361  or  +(370-2)-224694
> > Phone: +(370-2)-620861
> > Home address: Didlaukio 27-40, Vilnius 2057, Lithuania
> > Phone: +(370-2)-778743
> >
> >
> >
> >
> >
> >
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> --
>
>   Douglas J. Fox
>   Technical Support
>   Gaussian, Inc.
>   [email-masked]
>
>